JP2007093440A - Pcb analysis method, pcb analysis sample inlet device, and pcb analyzer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a PCB analysis method, which is a method for analyzing a sample containing PCB using capillary gaschromatograph, capable of quickly and accurately detecting/quantifying the PCB, with very low contamination of the separation column or the detector, and to provide a PCB analyzer used for the method. <P>SOLUTION: The temperature of a gasifying part of a sample inlet device is made lower than the gasification temperature of the solvent of the sample. After the sample is injected, the temperature is increased, until the gasification of the PCB in the sample. After it is kept for the time required for gasification of the PCB, the temperature is decreased below the gasification temperature of the solvent of the sample, and the contamination components in the sample are kept remaining in the gasification part. This PCB analyzer comprises at least the PCB analysis sample inlet device used for the PCB analysis method, the capillary column chromatograph equipped with the PCB analysis sample inlet device, and the detector. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a PCB analysis method for analyzing polychlorinated biphenyls (PCB) in insulating oil using a capillary gas chromatograph, a sample introduction device for PCB analysis, and a PCB analysis device.

Polychlorinated biphenyls (hereinafter referred to as “PCB”) have been widely used as electrical insulation materials such as transformers and capacitors, and heat media because of their high stability and insulation properties. Production and use were prohibited due to the confirmed hazards. PCB is regulated as a representative chemical substance of persistent organic pollutants that have persistent properties, remain in the environment, accumulate in living organisms through the food chain, and affect human health and ecosystems. In addition, it is obliged to store waste containing PCBs so as not to hinder the maintenance of the living environment until they are properly treated.
However, PCB waste that has been stored without proper treatment has been regarded as a problem of loss or leakage due to prolonged storage. In 2001, “Promotion of proper treatment of polychlorinated biphenyl waste” The Special Measures Law (PCB Special Measures Law) was enforced. The PCB Special Measures Law mandates proper disposal of all PCB waste within 15 years.

  For example, in the case of insulating oil, in addition to stored insulating oil, alternative insulating oil that has been replaced in a transformer that has used PCB as insulating oil in the past is also reduced to a small amount of PCB remaining in the transformer. It is known that it is contaminated, and it is necessary to inspect a large amount of PCB concentration, including alternative insulating oil in such a transformer, and to clarify the necessity of processing quickly. In addition, it is also very important to inspect the PCB waste concentration after processing and the PCB concentration in the environment after processing.

  As a conventional PCB analysis method, for example, a high resolution gas chromatograph-high resolution mass spectrometry (HRGC-HRMS) or a gas chromatograph method with an electron capture detector (GC-ECD method) is used as an official method. (Refer nonpatent literature 1). These methods have high resolution and a low quantification limit, but have a problem that the time required for analysis is long, the operation of a sample for removing contaminant components that interfere with analysis is complicated, and the cost burden is large.

  By the way, when analyzing insulating oil using a gas chromatograph, contaminants contained in the insulating oil significantly contaminate the separation column and analyzer, making long-term analysis and stable analysis difficult. There is a problem of becoming. For this reason, the method of removing the contaminating component contained in the said insulating oil by pre-processing is calculated | required.

  As a simple and inexpensive pretreatment method for these problems, for example, a method of introducing a test substance diluted with a non-polar non-polar solvent into a gas chromatograph has been proposed (see Patent Document 1). Yes. According to this method, the absolute amount of contaminant components introduced into the gas chromatograph can be reduced regardless of the type of test substance, but it is not possible to prevent contamination of the separation column and detector itself.

  On the other hand, a method has been proposed in which PCB extracted from a test substance using a polar solvent is passed through a reverse-phase solid-phase extractor and transferred to a volatile solvent to prepare a sample (see Patent Document 2). According to this method, contaminant components composed of aliphatic hydrocarbons and alicyclic hydrocarbons are removed, but polycyclic aromatic hydrocarbons, pigments, and other components added in the manufacturing process are not completely removed. . When such a sample is injected into a capillary gas chromatograph by, for example, a splitless injection method in which the temperature of the sample injection port is kept high or a cold on-column injection method, a separation column, a directly connected mass analyzer, etc. It is difficult to prevent contamination inside the detector.

  Therefore, in a method of analyzing a sample containing PCB using a capillary gas chromatograph, PCBs can be detected and quantified quickly and with high accuracy, with very little contamination of the separation column and detector, regardless of the type of test substance. The present situation is that a new PCB analysis method and a PCB analysis apparatus used in the method have not been provided.

JP 2004-61485 A JP 2000-88825 A “Rules for Analyzing Polychlorinated Biphenyl (PCB) in Insulating Oil” (Edited by the Electric Technical Standards Investigation Committee, published by the Japan Electric Association, issued on September 30, 1991)

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention relates to a method for analyzing a PCB-containing sample using a capillary gas chromatograph, and a PCB analysis method capable of detecting and quantifying PCB quickly and accurately with very little contamination of separation columns and detectors. An object of the present invention is to provide a PCB analyzer used in the method.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, when analyzing a sample containing PCB using a capillary gas chromatograph, the temperature of the sample introduction device for injecting the sample is controlled and analyzed. Send only the target PCB (especially PCB with a lot of chlorine contained in insulating oil and used industrially to 7 or less) to the separation column, and put other contaminants other than PCB into the sample introduction device. It was found that by contriving the residue, the contamination of the separation column and the detector can be prevented regardless of the type of the test substance, and PCB can be detected and quantified quickly and with high accuracy, and the present invention has been completed.

This invention is based on the said knowledge by this inventor, and as a means for solving the said subject, it is as follows. That is,
<1> The temperature of the gasification section in the sample introduction device of the capillary gas chromatograph is
When the sample is injected, the temperature is lower than the vaporization temperature of the solvent of the sample,
After injecting the sample, it is raised to a temperature at which PCB in the sample evaporates,
After holding the time necessary for the PCB to evaporate, it is lowered to below the vaporization temperature of the solvent of the sample,
It is a PCB analysis method characterized in that contaminant components in the sample remain in the gasification section. In the PCB analysis method according to <1>, the temperature of the gasification unit is set to be lower than the vaporization temperature of the solvent of the sample when the sample is injected, and the PCB in the sample is vaporized after the sample is injected. To a temperature required to evaporate the PCB, and then lowered to a temperature lower than the vaporization temperature of the solvent of the sample to leave the contaminating component in the sample in the gasification section, Only the vaporized PCB in the sample is sent to the separation column, and the contaminant components that have not been vaporized are prevented from flowing into the separation column and the detector. As a result, PCB detection / quantification is performed quickly and with high accuracy.
<2> The PCB analysis method according to <1>, wherein the temperature of the gasification section is increased to 170 ° C. In the PCB analysis method according to <2>, in order to raise the temperature of the gasification section to 170 ° C., only PCB having a large number of chlorine contained in the insulating oil is mainly vaporized, Sent to a separation column. As a result, PCB detection / quantification is performed quickly and with high accuracy.
<3> The sample according to any one of <1> to <2>, wherein the sample is injected into an exchangeable micro container provided in the gasification unit, and the contaminating component in the sample remains in the micro container. It is a PCB analysis method of description. In the PCB analysis method according to <3>, since the sample is injected into the micro container provided in the gasification unit, the contaminated components that have not been vaporized remain in the micro container. By exchanging the micro container in which the contaminating component remains, the contaminating component is easily removed. As a result, the PCB analysis is continuously performed quickly and efficiently.

<4> The PCB analysis method according to any one of <1> to <3>, wherein the sample is obtained by liquid-liquid extraction of PCB in a test substance with a polar solvent. In the PCB analysis method according to <4>, since the sample is obtained by liquid-liquid extraction of PCB in the test substance with a polar solvent, the sample is prepared very easily regardless of the type of the test substance. As a result, PCB detection / quantification is performed quickly and efficiently.
<5> The PCB analysis method according to <4>, wherein the polar solvent is dimethyl sulfoxide (DMSO).
<6> A sample is obtained by liquid-liquid extraction of PCB in a test substance with a polar solvent, the polar solvent containing the extracted PCB is subjected to solid phase extraction with an adsorbent, and components adsorbed on the adsorbent are volatile organically extracted. The PCB analysis method according to any one of <1> to <3>, wherein the PCB analysis method is obtained by dissolving in a solvent. In the PCB analysis method according to <6>, a sample is obtained by subjecting PCB in a test substance to liquid-liquid extraction with a polar solvent, solid phase extraction of the polar solvent containing the extracted PCB with an adsorbent, A component adsorbed on the adsorbent is dissolved in a volatile organic solvent. As a result, PCB can be detected and quantified quickly and efficiently with high accuracy.
<7> The PCB analysis method according to <6>, wherein the polar solvent is dimethyl sulfoxide (DMSO).
<8> The PCB analysis method according to any one of <6> to <7>, wherein the adsorbent is a polymer-based reversed-phase film type adsorbent.

<9> The PCB analysis method according to any one of <1> to <8>, wherein the test substance is an insulating oil.
<10> The PCB analysis method according to any one of <1> to <9>, wherein the test substance is a PCB contaminant.

<11> After the PCB in the sample is separated by capillary gas chromatography, the PCB concentration in the sample is determined by at least one of the tandem mass spectrometry (MS / MS) method and the negative ion chemical ion (NCI / MS) method. The PCB analysis method according to any one of <1> to <10>, wherein the analysis is performed by
<12> The PCB analysis method according to <11>, wherein the PCB concentration is calculated from the peak area of the chromatogram.

<13> Used in the PCB analysis method according to any one of <1> to <12>,
The temperature of the gasification part in the sample introduction device of the capillary gas chromatograph,
When the sample is injected, the temperature is lower than the vaporization temperature of the solvent of the sample,
After injecting the sample, it is raised to a temperature at which PCB in the sample evaporates,
After holding the time necessary for the PCB to evaporate, it is lowered to below the vaporization temperature of the solvent of the sample,
A PCB analysis sample introduction apparatus, comprising temperature control means for allowing contaminant components in the sample to remain in the gasification section. In the PCB analysis sample introduction device described in <13>, the temperature of the gasification unit is set to be lower than the vaporization temperature of the solvent of the sample at the time of injection of the sample, and after the sample is injected, The temperature of the PCB is increased to a temperature at which the PCB is vaporized, and is maintained for a time necessary for the PCB to be vaporized. Then, the temperature is lowered to a temperature lower than the vaporization temperature of the solvent of the sample, so Since the temperature control means is provided, the contaminated components that have not been vaporized are prevented from flowing into the separation column and the detector. As a result, contamination of the separation column and detector is prevented, and PCB detection and quantification are performed quickly and with high accuracy.
<14> The sample introduction device for PCB analysis according to <13>, wherein the gasification unit includes a replaceable micro container. In the PCB analysis sample introduction device described in <14>, the micro container in which the contaminating component remains and the new micro container are exchanged. As a result, the next analysis can be performed by exchanging the micro container. For example, PCB analysis is continuously and efficiently performed.
<15> From <13> to <13>, wherein the micro container has an opening into which a sample is introduced at one end, a bottom for holding the sample at the other end, and at least one hole on a side surface. 14> The sample introduction device for PCB analysis according to any one of the above. In the PCB analysis sample introduction device described in <15>, the micro container has an opening through which the sample is introduced at one end, a bottom for holding the sample at the other end, and a side surface. Since it has at least one hole, the vaporized component is efficiently diffused. As a result, PCB can be detected and quantified quickly and accurately.
<16> The sample introduction device for PCB analysis according to any one of <13> to <15>, further including means for automatically exchanging at least one of a gasification unit and a micro container.

<17> A PCB analysis device comprising at least a capillary column chromatograph including the PCB analysis sample introduction device according to any one of <13> to <16>, and a detector.
<18> The PCB analyzer according to <17>, wherein the detector is a mass spectrometer.

  According to the present invention, in a method for analyzing a sample containing PCB using a capillary gas chromatograph, a PCB analysis method capable of detecting and quantifying PCB quickly and accurately with very little contamination of a separation column and a detector, A PCB analyzer used in the method can be provided.

(PCB analysis method, PCB analysis sample introduction device, PCB analysis device)
The sample analysis apparatus for PCB analysis of the present invention is used in the PCB analysis method of the present invention, and the temperature of the gasification part in the sample introduction apparatus of a capillary gas chromatograph is set at the time of injection of the sample by the solvent of the sample. After the sample is injected, the temperature is raised to a temperature at which PCB in the sample is vaporized, held for a time necessary for the PCB to vaporize, and then lowered to below the vaporization temperature of the solvent of the sample, There is at least temperature control means for causing the contaminant components in the sample to remain in the gasification section.
The PCB analysis apparatus of the present invention includes at least a capillary column chromatograph provided with the PCB analysis sample introduction device and a detector, and includes other devices appropriately selected.

In the PCB analysis method of the present invention, the temperature of the gasification section in the sample introduction device of a capillary gas chromatograph is set to be lower than the vaporization temperature of the solvent of the sample at the time of injection of the sample. The temperature is increased to a temperature at which PCB in the sample is vaporized, and is maintained for a time necessary for the PCB to be vaporized, and then lowered to a temperature lower than the vaporization temperature of the solvent of the sample, so that contaminant components in the sample remain in the gasification unit. Including other processes selected as appropriate.
The PCB analysis method of the present invention can be preferably carried out using the PCB analysis sample introduction apparatus of the present invention, and can be preferably carried out using the PCB analysis sample introduction apparatus of the present invention. The description of the PCB analysis apparatus of the present invention will be made clear through the description of the PCB analysis material introduction apparatus of the present invention and the PCB analysis apparatus of the present invention.

<Sample introduction device for PCB analysis>
A sample analysis apparatus for PCB analysis of the present invention used in the PCB analysis method of the present invention will be described with reference to FIG.
The PCB analysis sample introduction apparatus 10 includes a septum 20 at one end (here, the upper end) of a cylindrical outer frame 11, and a carrier gas inlet 30 and a septum purge 40 are provided in communication with each other. A split purge 50 is provided. Inside the outer frame 11, a gasification part 62 is defined by an inlet liner (insert) 60. The inlet liner (insert) 60 has an O-ring (not shown) formed by a cap nut 12. And is detachably connected to the outer frame 11.
A capillary column 80 is connected to one end (here, the lower end) of the inlet liner (insert) 60.
The inlet liner (insert) 60 includes a micro container holding portion 61 on which the micro container 70 can be placed. The micro container holding part 61 is composed of two or more protrusions and does not block the gas flow inside the inlet liner (insert) 60 even when the micro container 70 is installed. .

<< Micro container >>
The micro container 70 can be installed inside the gasification unit 62, has an opening into which a sample is introduced at one end, and has a bottom portion for holding the sample at the other end. The structure is not particularly limited as long as it has a structure that can diffuse at least from the opening, and can be appropriately selected according to the purpose, but is preferably exchangeable.

Examples of the material of the micro container 70 include glass, and among these, heat resistant glass and quartz glass are preferable.
As the shape of the micro container 70, for example, a cylindrical shape is preferable.

  The micro container 70 preferably has at least one hole on the side surface. Although there is no restriction | limiting in particular as a shape of the said hole part, It is preferable that it is a shape which can be formed easily in manufacture of the said micro container.

The sample analysis apparatus for PCB analysis includes means for automatically replacing at least one of the gasification unit 62, that is, the inlet liner (insert) 11 that defines the gasification unit, and the micro container 70. Is preferred.
Examples of means for automatically exchanging at least one of the inlet liner (insert) 11 and the micro container 70 include an apparatus including a robot system operable in the XYZ axial directions.

<< Temperature control means >>
A temperature control means 90 is provided at one end (here, the lower end) of the PCB analysis sample introduction apparatus 10.
The temperature control means 90 sets the temperature of the gasification unit 62 to be lower than the vaporization temperature of the solvent of the sample at the time of injection of the sample, and rises to a temperature at which PCB in the sample is vaporized after the sample is injected. Then, after holding the time necessary for the PCB to evaporate, the sample is lowered to a temperature lower than the vaporization temperature of the solvent of the sample, and control is performed so that the contaminating component in the sample remains in the gasification unit.
Here, the temperature in the gasification unit 62 and the temperature in the micro container 70 are substantially the same, that is, the temperature control means 90 sets the temperature in the micro container 70 at the time of injection of the sample. The temperature of the sample is lower than the vaporization temperature of the solvent, and after the sample is injected, the temperature of the PCB in the sample is increased to a temperature at which the PCB is vaporized. The temperature is lowered to below the temperature, and control is performed so that the contaminating components in the sample remain in the micro container 70.

  Further, the temperature control means 90 maintains the temperature inside the gasification unit 62 and the micro container 70 at a temperature lower than the vaporization temperature of the solvent of the sample, at least until the PCB analysis is completed. It is preferable that the temperature can be controlled, and it is more preferable that the temperature can be controlled until a new sample is injected as the next analysis.

The temperature control unit 90 is not particularly limited as long as the above-described temperature control is possible, and can be appropriately selected according to the purpose. However, at least a sensor capable of detecting temperature, a heating unit, and a cooling unit are provided. These are preferable, and those which are automatically controlled and operated by a program or the like are more preferable.
Examples of the heating method in the heating means include electromagnetic wave heating, induction heating, resistance heating and the like.
Examples of the cooling method in the cooling means include air cooling (air blowing, etc.), cooling with a refrigerant (liquefied nitrogen, liquefied carbon dioxide, etc.), electronic cooling, and the like.

<Sample introduction method>
Examples of the method for injecting the sample into the PCB analysis sample introduction device include a method for injecting the sample into the gasification unit 62 using a syringe or the like equipped with a needle that can penetrate the septum 20. At this time, it is preferable that the sample is injected and held in the micro container 70.
At the time of injection of the sample, the inside of the gasification unit 62 and the micro container 70 is maintained below the vaporization temperature of the solvent of the sample. Flash can be prevented.

After the sample is injected into the gasification unit 62 or the micro container 70, the internal temperatures of the gasification unit 62 and the micro container 70 are raised to a temperature at which PCB in the sample is vaporized.
At this time, the inside of the gasification unit 62 and the micro container 70 is preferably heated at a rapid and constant heating rate, and the heating rate is, for example, 0.1 to 20 ° C./second. 16 ° C./second is preferable.
The temperature at which PCB is vaporized includes, for example, 150 to 310 ° C. By increasing the internal temperature of the micro container to 310 ° C, PCB having a high chlorine number can be vaporized, but the test substance is insulated. In the case of oil, a viewpoint that selectively separates PCBs mainly containing a large amount of 7 or less chlorine in the insulating oil and efficiently analyzes them, and a viewpoint that suppresses mixing of high-boiling contaminants Therefore, it is preferable to increase the internal temperature of the micro container to 220 ° C., and more preferably to 170 ° C.

  For example, the PCB component contained in the insulating oil of the capacitor / transformer is said to be 20% for KC-300, 30% for KC-400, and 50% for KC-500. The PCB isomer distribution (weight ratio) contained in these is shown in Table 1 below.

(Source: Takuzo Takatsuki et al., “Detailed analysis method of all isomers of polychlorinated biphenyls (PCBs) using various cleanup methods and HRGC / HRMS”, Environmental Chemistry, Vol. 5, No. 3, pp. 647- 675, 1995)

  The vaporized solvent in the sample is removed at 1 to 600 mL / min from the split purge 50 of the PCB analysis sample introduction apparatus.

Next, the internal temperatures of the gasification unit 62 and the micro container 70 are maintained at a temperature at which the PCB is vaporized for a time necessary for the PCB to vaporize, thereby sufficiently vaporizing the PCB in the sample.
The time required for the PCB to vaporize is preferably 0.5 to 15 minutes, and preferably 10 minutes. If this time is less than 0.5 minutes, the amount of PCB sent to the column may be small and analysis may be difficult. If it exceeds 15 minutes, the contaminated component in the sample is sent to the column. , May contaminate the column.

Subsequently, the internal temperature of the gasification unit 62 and the micro container 70 is lowered to a temperature lower than the vaporization temperature of the solvent of the sample, and the high boiling point component (contaminating component) that has not been vaporized is gasified as a liquid or a solid. It remains in at least one of the part 62 and the micro container 70.
At this time, the inside of the gasification unit 62 and the micro container 70 is preferably cooled at a constant cooling rate, and the cooling rate is preferably 1 ° C./second or more, preferably 5 ° C./second. More preferably.

  The sample is injected into the micro container, and further, the PCB is vaporized in the micro container, and then rapidly cooled, whereby the contaminating component can be reliably left in the micro container, Contaminating components can be removed together with the micro container, and further, the next analysis can be quickly performed when the analysis is repeatedly performed.

<< Sample >>
Examples of the sample include a sample obtained by liquid-liquid extraction of PCB in the test substance with a polar solvent, and the polarity containing PCB extracted by liquid-liquid extraction of the PCB in the test substance with a polar solvent. Examples include a sample obtained by solid-phase extraction of a solvent with an adsorbent, and a component adsorbed on the adsorbent being dissolved in a volatile organic solvent.

  The polar solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dimethyl sulfoxide (DMSO), dimethylformamide, acetonitrile, sulfolane, 1,3-dimethyl-2-imidazolidinone and the like. Among these, dimethyl sulfoxide (DMSO) is preferable.

  In the liquid-liquid extraction, the mixing ratio (mass ratio) of the test substance and the polar solvent is preferably (the test substance) :( the polar solvent) = 1: 1 to 1:10.

The adsorbent is not particularly limited as long as it can adsorb PCB in the polar solvent and can be dissolved in a volatile solvent, and can be appropriately selected according to the purpose. In particular, an adsorbent made of polystyrene-tetrafluoroethylene resin (PTFE) or the like can be mentioned.
There is no restriction | limiting in particular as a shape of the said adsorbent, According to the objective, it can select suitably, For example, a column type, a disk type | mold (film | membrane type), etc. are mentioned.

The volatile solvent is not particularly limited as long as PCB adsorbed on the adsorbent can be dissolved therein, and can be appropriately selected according to the purpose. Examples thereof include n-hexane, toluene, and dichloromethane. Among these, n-hexane is preferable.
When the solvent of the sample is n-hexane, the temperature of the inlet at the time of introducing the sample is preferably about 60 ° C.

  As a method for preparing a sample obtained by liquid-liquid extraction of PCB in the test substance with a polar solvent, for example, the polar solvent is added to the test substance and stirred, and then centrifuged to collect a polar solvent layer. Can be prepared. The polar solvent layer thus obtained may be further prepared by adding the polar solvent and stirring and then performing centrifugation.

PCB in the test substance is liquid-liquid extracted with a polar solvent, the polar solvent containing the extracted PCB is solid-phase extracted with an adsorbent, and components adsorbed on the adsorbent are transferred to a volatile organic solvent. As the method for preparing the sample, for example, the polar solvent layer obtained by adding the polar solvent to the test substance and stirring and then centrifuging is added and stirred, and this is adsorbed to the adsorption material. It can be prepared by loading the agent and immersing the adsorbent in the volatile solvent.
For example, anhydrous sodium sulfate is preferably added to the sample to remove moisture.

The test substance is not particularly limited as long as it is a substance (PCB contaminant) that may contain at least PCB, and can be appropriately selected according to the purpose. For example, insulating oil, oil other than insulating oil (For example, vegetable oils, animal oils, synthetic oils, mineral oils, etc.), factory wastewater, soil, exhaust gas, animal blood and body fluids, wastes such as members used in the treatment of insulating oils, and the like. Among these, insulating oil is preferably exemplified.
As said insulating oil, the insulating oil after performing PCB decomposition processes, such as a dechlorination process, is also mentioned suitably.

<PCB analyzer>
The PCB analyzer includes at least a capillary column chromatograph including the PCB analysis sample introduction device 11 and the detector, and further includes a carrier gas cylinder, a carrier gas introduction unit, a flow rate control device, and a recording device. It is preferable.

PCB vaporized from the sample injected into the PCB analysis sample introduction apparatus 11 is carried by the carrier gas flowing in from the carrier gas inlet 30, flows into the capillary column (separation column) 80, and is separated into isomers. Then, it is introduced into the detector such as a mass spectrometer.
For example, helium is preferable as the carrier gas.
The flow rate of the carrier gas is preferably a flow rate in a region where the theoretical plate equivalent height (HETP) of the capillary column to be used is the lowest.

  Since the contaminating component in the sample remains in either the gasification unit 62 or the micro container 70, the capillary column (separation column) 80 and the inside of the detector are not contaminated.

The capillary column (separation column) 80 preferably includes a column oven, and the temperature is controlled by the column oven.
The column oven is not particularly limited as long as the temperature of the entire length of the capillary column (separation column) 80 can be controlled, and can be appropriately selected according to the purpose.
The material of the capillary column (separation column) 80 is not particularly limited as long as the isomers of the PCB can be separated, and can be appropriately selected according to the purpose. For example, an inert metal, glass, Quartz etc. are mentioned.

The detector is not particularly limited as long as it can detect the isomers of PCB and analyze the mass of each isomer, and can be appropriately selected according to the purpose. Examples include a polar mass spectrometer.

<PCB detection method>
As the method for detecting the PCB, for example, the isomer of the PCB is ionized in the detector and analyzed by a tandem mass spectrometry (MS / MS) method, a negative ion chemical ionization (NCI) method, etc. Can be recorded as a chromatogram.
Among these, a tandem mass spectrometry (MS / MS) method is preferable, and a multiple reaction monitoring (MRM) method is preferable as a detection method.

  As a method for confirming the PCB by the PCB detection method, for example, a standard sample to which a PCB isomer is added at a known concentration is used, and the retention times of the PCB isomers detected from the sample match. The method of confirming is mentioned.

  Examples of the standard sample include Kanechlor (KC-300, KC-400, KC-500, KC-600) in the sample solvent (polar solvent or volatile solvent) when the test substance is an insulating oil. , KC-1000) at a constant concentration.

  The chromatogram is prepared using the standard sample, the peak area of the PCB isomer in the canechlor is plotted on the vertical axis of the chromatogram, and the known PCB isomer in the standard sample is plotted on the horizontal axis. A calibration curve is created by taking the concentration, and based on the calibration curve, the concentration of each PCB isomer in the data can be determined based on a chromatograph created from the sample.

(Preparation of calibration curve using standard sample)
As the standard sample, dimethyl sulfoxide (DMSO) added with Kanechlor (KC-300, KC-400, KC-500, KC-600, KC-1000) as a PCB, and the PCB analysis method, A calibration curve was created.

  2 μL of the standard sample was injected into the micro container 70 of the PCB analysis sample introduction apparatus 10 shown in FIG. The temperature in the micro container is set to 80 ° C. when the standard sample is injected. After the standard sample is introduced, the micro sample is heated to 280 ° C. at 5 ° C./second, held at 280 ° C. for 5 minutes, and then 0.7 ° C. / Cooled to 80 ° C. in seconds.

  Helium was introduced from the carrier gas inlet 30 at a flow rate of 3 mL / min as the carrier gas. The flow rate of the split purge 50 was 0 mL / min from the start of measurement to 340 seconds, and thereafter 20 mL / min to remove the solvent in the sample.

  The capillary column (separation column) 80 is held at 150 ° C. for 2 minutes by the column oven, heated to 170 ° C. at 20 ° C./minute, held at 170 ° C. for 3 minutes, and then 200 ° C. at 20 ° C./minute. And heated at 200 ° C. for 2 minutes, then heated to 310 ° C. at 20 ° C./minute, held at 310 ° C. for 1 minute, and the PCB that flowed in was separated.

A tandem mass spectrometer was used as a detector, and the PCB was ionized by an electron impact ionization (EI) method. The ionization voltage was 70 eV, the ionization current was 300 μA, the ion source temperature was 220 ° C., and the detection voltage was 1600 V.
The ionized PCB was detected by a multiple reaction monitoring (MRM) detection method to obtain a chromatogram. The conditions for the multiple reaction monitoring (MRM) detection method are shown in Table 2 below.

  From the chromatogram, areas were obtained for peaks within the retention times shown in Table 3 below, and calibration curves shown in FIGS. 3 to 7 were obtained.

  From the results of FIGS. 3 to 7, it can be seen that according to the PCB analysis method of the present invention, a correlation coefficient of 0.9 or more is obtained between the addition amount and the detection amount in the standard sample. Moreover, the lower limit value of the concentration that can be measured is 0.5 ppm for each kanechlor, indicating that high resolution can be obtained.

  According to the PCB analysis method of the present invention using the sample introduction device for PCB analysis and the PCB analysis device of the present invention, the PCB concentration can be detected and quantified with high accuracy, and the capillary column (separation column), Since contamination of the detector is prevented, stable measurement can be repeatedly performed.

  Hereinafter, although the Example of this invention is described, this invention is not limited to this Example at all.

Example 1
As the test substance, 43 kinds of used insulating oils were used, and the PCB concentration was measured by the PCB analysis method of the present invention, and the measurement was performed by the official method (HRMS), and the results were compared.

-Sample preparation-
As a sample for the PCB analysis method of the present invention, 0.5 mL of dimethyl sulfoxide was added to 0.5 g of the insulating oil, stirred for 2 minutes, centrifuged at 3000 rpm for 2 minutes, and the dimethyl sulfoxide layer was collected. did.

-PCB separation-
The sample and 2 μL of the standard sample were respectively injected into the micro container 70 of the PCB analysis sample introduction apparatus 10 shown in FIG. The temperature in the micro container is set to 80 ° C. when the standard sample is injected. After the standard sample is introduced, the micro sample is heated to 280 ° C. at 5 ° C./second, held at 280 ° C. for 5 minutes, and then 0.7 ° C. / Cooled to 80 ° C. in seconds.

  Helium was introduced from the carrier gas inlet 30 at a flow rate of 3 mL / min as the carrier gas. The flow rate of the split purge 50 was 0 mL / min from the start of measurement to 340 seconds, and thereafter 20 mL / min to remove the solvent in the sample.

  The capillary column (separation column) 80 is held at 150 ° C. for 2 minutes by the column oven, heated to 170 ° C. at 20 ° C./minute, held at 170 ° C. for 3 minutes, and then 200 ° C. at 20 ° C./minute. And heated at 200 ° C. for 2 minutes, then heated to 310 ° C. at 20 ° C./minute, held at 310 ° C. for 1 minute, and the PCB that flowed in was separated.

-PCB detection and quantification-
A tandem mass spectrometer was used as a detector, and the PCB was ionized by an electron impact ionization (EI) method. The ionization voltage was 70 eV, the ionization current was 300 μA, the ion source temperature was 220 ° C., and the detection voltage was 1600 V.
The ionized PCB was detected by a multiple reaction monitoring (MRM) detection method to obtain a chromatogram. Based on the chromatogram, for 3 to 8 chlorinated products, the correlation with the measurement result by the official method was examined, and the concentration of each isomer was further measured. The results are shown in FIGS.

In Table 4, “-” indicates that the value is less than the lower limit of quantification, and the numbers in parentheses indicate the lower limit of detection and lower than the lower limit of quantification.

From the results shown in FIGS. 8 to 13 and Table 4, the results obtained by the PCB analysis method of the present invention and the results obtained by the official method obtained a very high correlation especially for the 5 chlorinated products and 6 chlorinated products, and the total peak of the chromatogram. The area was found to have a very high correlation with each isomer.
Moreover, according to the PCB analysis method of the present invention, the analysis could be continuously performed without contamination of the separation column. On the other hand, in the analysis by the official method, the separation column was contaminated, and one measurement cleaning was required.

(Example 2)
As the test substance, 3 mL of dimethyl sulfoxide was added to 0.75 g of insulating oil, stirred for 2 minutes, centrifuged at 3000 rpm for 2 minutes, and 1 mL of the dimethyl sulfoxide layer was collected. 9 mL of pure water was added here, and it stirred for 2 minutes with the vortex mixer. The obtained suspension was sample loaded onto an SDB-XC cartridge, dissolved in 1 ml of hexane, and anhydrous sodium sulfate was added to prepare a sample.
As the standard sample, KC-300, KC-400, KC-500, and KC-600 were used and prepared in the same manner as the sample.

  The sample and 3 μL of the standard sample were each injected into the micro container 70 of the PCB analysis sample introduction apparatus 10 shown in FIG. The temperature in the micro container is 60 ° C. when the standard sample is injected, and after the standard sample is introduced, it is heated to 280 ° C. at 5 ° C./second, held at 280 ° C. for 10 minutes, and then at 1 ° C./second. Cooled to 60 ° C.

  Helium was introduced as a carrier gas from the carrier gas inlet 30 at a flow rate of 0.8 mL / min. The flow rate of the split purge 50 was 100 mL / min to remove the solvent in the sample.

  The capillary column (separation column) 80 is held at 60 ° C. for 3 minutes by the column oven, heated to 200 ° C. at 15 ° C./min, further heated to 280 ° C. at 5 ° C./min, and 10 at 280 ° C. Hold for minutes to separate the PCB.

A tandem mass spectrometer was used as a detector, and the PCB was ionized by an electron impact ionization (EI) method. The ionization voltage was 70 eV, the ionization current was 300 mA, and the ion source temperature was 280 ° C.
The ionized PCB was detected by a multiple reaction monitoring (MRM) detection method under the conditions shown in Table 5 below, and a chromatogram was obtained for each. The results are shown in FIGS.

  As a result of comparing the concentration of PCB obtained from the peak area of the chromatogram of the standard data and the amount of added PCB, the PCB recovery rate by the sample preparation method in the PCB analysis method of the present invention is 85.6%. all right.

(Example 3)
The sample and 1 μL of the standard sample were analyzed in the same manner as in Example 2 except that the temperature of the gasification part (micro container) was raised to 170 ° C. and 220 ° C.
The results are shown in FIGS.

  From the results of FIGS. 20 and 21, it was found that the peak of the 8 chlorinated product (8Cl) does not appear when the temperature of the gasification part (micro container) is set to 170 ° C.

(Comparative Example 1)
In Example 2, the analysis was performed in the same manner as in Example 2 except that the sample inlet of the sample introduction apparatus was not cooled after heating.
As a result, noise in the chromatogram increased, and contamination was observed when the separation column was observed after analysis.

  The PCB analysis method of the present invention has very little contamination of separation columns and detectors regardless of the type of test substance, and can detect and quantify PCBs quickly and with high accuracy. It can be suitably used for detection and quantification of PCB contained in PCB-containing waste.

FIG. 1 is a cross-sectional view showing an example of a sample analysis apparatus for PCB analysis according to the present invention. 2 is a cross-sectional view of the A-A ′ plane of the PCB analysis sample introduction apparatus of FIG. 1. FIG. 3 is a calibration curve of a standard sample (KC-300) prepared by the PCB analysis method of the present invention. FIG. 4 is a calibration curve of a standard sample (KC-400) prepared by the PCB analysis method of the present invention. FIG. 5 is a calibration curve of a standard sample (KC-500) prepared by the PCB analysis method of the present invention. FIG. 6 is a calibration curve of a standard sample (KC-600) prepared by the PCB analysis method of the present invention. FIG. 7 is a calibration curve of a standard sample (KC-1000) prepared by the PCB analysis method of the present invention. FIG. 8 is a graph showing a correlation between a calibration curve obtained by the official method of 3-chlorine PCB (trichlorinated product) in Example 1 and a measurement result obtained by the PCB analysis method of the present invention. FIG. 9 is a graph showing the correlation between the calibration curve obtained by the official method of 4-chlorine PCB (4-chlorinated product) in Example 1 and the measurement result obtained by the PCB analysis method of the present invention. FIG. 10 is a graph showing the correlation between the calibration curve obtained by the official method of 5-chlorine PCB (pentachlorinated product) in Example 1 and the measurement result obtained by the PCB analysis method of the present invention. FIG. 11 is a graph showing the correlation between the calibration curve obtained by the official method of 6-chlorine PCB (6-chlorinated product) in Example 1 and the measurement result obtained by the PCB analysis method of the present invention. FIG. 12 is a graph showing the correlation between the calibration curve obtained by the official method of 7 chlorine PCB (7 chlorinated product) in Example 1 and the measurement result obtained by the PCB analysis method of the present invention. FIG. 13 is a graph showing the correlation between the calibration curve obtained by the official method of 8-chlorine PCB (8 chlorinated product) in Example 1 and the measurement result obtained by the PCB analysis method of the present invention. FIG. 14 is a chromatogram of 2-chlorine PCB (dichlorinated product) obtained in Example 2, with the upper part showing the sample and the lower part showing the result of the standard sample. FIG. 15 is a chromatogram of 3-chlorine PCB (trichlorinated product) obtained in Example 2, in which the upper part shows the result of the sample and the lower part shows the result of the standard sample. FIG. 16 is a chromatogram of 4-chlorine PCB (4-chlorinated product) obtained in Example 2, wherein the upper part shows the result of the sample and the lower part shows the result of the standard sample. FIG. 17 is a chromatogram of 5-chlorine PCB (pentachlorinated product) obtained in Example 2, wherein the upper part shows the result of the sample and the lower part shows the result of the standard sample. FIG. 18 is a chromatogram of 6-chlorine PCB (6-chlorinated product) obtained in Example 2, with the upper part showing the sample and the lower part showing the result of the standard sample. FIG. 19 is a chromatogram of 7-chlorine PCB (7 chlorinated product) obtained in Example 2, wherein the upper part shows the result of the sample and the lower part shows the result of the standard sample. FIG. 20 shows the analysis result of 1 μL of the insulating oil of Example 3, the upper part shows the chromatogram when the temperature is raised to 170 ° C. in the gasification part (in the micro container), the middle part and the lower part are 1 to 10 chlorinated substances. Is a sample mass spectrum in which 25 ppm is added. The middle part shows the result when the gasification part (inside the micro container) is heated to 220 ° C., and the lower part shows the result when the temperature is raised to 170 ° C. Each is shown. FIG. 21 is a mass spectrum showing the analysis result of the standard sample of Example 3. The upper part shows the result of raising the temperature of the gasification part (inside the micro container) to 220 ° C., and the lower part shows the result of raising the temperature to 170 ° C. .

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Sample introduction apparatus 11 Outer frame 12 Cap nut 20 Septum 30 Carrier gas inlet 40 Septum purge 50 Split purge 60 Inlet liner (insert)
61 Micro container holding part 62 Gasification part 70 Micro container 80 Capillary column (separation column)
90 Temperature control means

Claims (14)

The temperature of the gasification part in the sample introduction device of the capillary gas chromatograph,
When the sample is injected, the temperature is lower than the vaporization temperature of the solvent of the sample,
After injecting the sample, the temperature is raised to a temperature at which polychlorinated biphenyls (PCB) in the sample are vaporized,
After holding the time necessary for the PCB to evaporate, the PCB is lowered to below the vaporization temperature of the solvent of the sample,
A PCB analysis method characterized in that contaminant components in the sample remain in the gasification section.   The PCB analysis method according to claim 1, wherein the temperature of the gasification section is increased to 170 ° C.   The PCB analysis method according to claim 1, wherein the sample is injected into a replaceable micro container provided in the gasification unit, and a contaminating component in the sample is left in the micro container.   The PCB analysis method according to any one of claims 1 to 3, wherein the sample is obtained by subjecting PCB in a test substance to liquid-liquid extraction with a polar solvent.   A sample is obtained by liquid-liquid extraction of PCB in a test substance with a polar solvent, solid phase extraction of the polar solvent containing the extracted PCB with an adsorbent, and conversion of the components adsorbed on the adsorbent into a volatile organic solvent. The PCB analysis method according to claim 1, which is dissolved.   The PCB analysis method according to claim 5, wherein the adsorbent is a polymer-based reversed-phase film type adsorbent.   The PCB analysis method according to claim 1, wherein the test substance is an insulating oil.   The PCB in the sample is separated by capillary gas chromatography, and then the concentration of PCB in the sample is analyzed by at least one of a tandem mass spectrometry (MS / MS) method and a negative ion chemical ionization (NCI) method. The PCB analysis method according to any one of 1 to 7.   The PCB analysis method according to claim 8, wherein the PCB concentration is calculated from the peak area of the chromatogram. It is used for the PCB analysis method according to any one of claims 1 to 9,
The temperature of the gasification part in the sample introduction device of the capillary gas chromatograph,
When the sample is injected, the temperature is lower than the vaporization temperature of the solvent of the sample,
After injecting the sample, the temperature is raised to a temperature at which polychlorinated biphenyls (PCB) in the sample are vaporized,
After holding the time necessary for the PCB to evaporate, the PCB is lowered to below the vaporization temperature of the solvent of the sample,
A sample introduction apparatus for PCB analysis, comprising temperature control means for causing contaminant components in the sample to remain in the gasification section.   The sample introduction device for PCB analysis according to claim 10, further comprising a replaceable micro container in the gasification section.   The micro container has an opening for introducing a sample at one end, a bottom for holding the sample at the other end, and at least one hole on a side surface. The sample introduction apparatus for PCB analysis as described.   The sample introduction device for PCB analysis according to any one of claims 10 to 12, further comprising means for automatically exchanging at least one of a gasification section and a micro container.   A PCB analyzer comprising at least a capillary column chromatograph provided with the sample introduction device for PCB analysis according to claim 10 and a detector.